Surface-active agent



Patented Dec. 7, 1943 SURFACE-ACTIVE AGENT Joseph B. Dickey and Anthony Loria, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application August 15, 1941,

, Serial No. 407,066

1 Claim. (01'. 260-457) This invention relates to the preparation and use of new organic compounds useful as surfaceactive agents andmore particularly to derivatives of phosphonic acids having high chemical stability and inertness to hard water.

The principal object of the invention is the production of a new class of organic chemical compounds which are useful as surface-active agents such as wetting agents, dispersing or emulsifying agents, penetrating agents, detergents and the like. A further object is to provide compounds which are useful as textile lubricants and anti-statics. A still further object is to provide a new class of derivatives of phosphonic acid. Other objects will appear hereinafter.

We have found that phosphonic acids having the general formula (A) on lat-R o=ton and RI 011 OH Beat- R H o m wherein R, R, RP and R are substituents selected from the group consisting of hydrogen, alkyl, aryl, naphthenyl, alkaryl and heterocycllc groups, when reacted with suitable sulfating agents give compounds having the formulae (1) OSOaH R- -R o= -on H (II) R EH R*-C-;P\- (R 0 on a: lsom and (111 RI 0H OSOJH R- --PC-R soul which are useful for the above-mentioned purposes and constitute new chemical compounds.

.tetrahydrofurfurylamine,

The carbinol group of II can be acylated, alkylated, phosphated, etc.. if desired. Acids of types I, II, and III can be wholly or partially neutralized with any desired organic or inorganic base such as, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium, tetramethylammonium hydroxide, triethylcetylammonlum hydroxide, trimethylbenzylammon'ium hydroxide, tributyltetrahydrofurfurylammonium hydroxide, mono-, diand tri-ethanolamine, amylamine, oleylamine, naphthenylamine, tetrahydrofurfurylamine, ditetrahydrofurfurylamine, diethyldiethylcyclohexylamine, beta-hydroxy-beta-ethoxy-beta-ethoxyethylamine, ethylenediamine, morpholine. piperazine, benzylamine, etc. In the preparation of these salts one or more bases may be used.

The intermediates used may be prepared as described in Friend's Textbook of Inorganic Chemistry," II, Part III, Chapter 1': J. Am. Chem. Soc., 43, 1928; ibid, 44, 2530; Compt. rend, 134, 847; Ann. chim. phys. (8) 3, 347: Comp, rend., 136, 234; ibid., 133, 219; and in the following U. S. Patents Nos. 2,279,501, 2.279.502. 2.286.792.

The acids (A) and (B) are sulfated by reacting with a sulfating agent such as oleum. sulfuric acid, sulfur trioxide, pyrosulfuric acid, dioxanesulfur trioxide complex, chlorosulfonic acid, sulfuryl chloride, sulfamidyl chloride, etc. These reactions may be carried out in a solvent.

The products of this invention give calcium and magnesium salts which are sufllciently soluble in water to enable one to use these compounds in hard water without the formation of the objectionable precipitates obtained with soap. Because of this property many of the products of this invention are valuable for many household purposes, such as the cleansing of cloth, dishes, and the like. The products of this invention can also be used with advantage for practically any purpose where a "surface-active" compound is needed; for example, as dispersing, wetting, emulsifying, and cleansing agents, as textile assistants, and dye-dispersing agents. The products of this invention are oi especial value for lubricating textiles and are particularly valuable for use on textiles including cellulose acetate where an antistatic agent is required.

In the following examples and description, we have included several of the preferred embodiments of our invention, but they are included merely for purpose of illustration and not as a limitation thereof.

Pnanaurou or rm: Comomms Example 1 One mole of 2-hydroxyheptane phosphinate- 2 is placed in a flask fitted with a stirrer and dropping tunnel and one mole of chlorosulionic acid is added'dropwise with stirring. Hydrogen chloride is evolved and the reaction is completed by warming. Water is then added and any mono, di, or trl salt desired is prepared by adding the required amount base. The 2-suliatoheptane phosphinic acid-2 has the formula OSOaH CIHIP' CH:

Example 2-2-alpha-sul!atohcptane-2-alphahy-- droxyheptane phosphinic acid One mole of 2-bis-alpha-hydroxyheptane phosphinic acid is reacted as in Example 1 with one mole of chlorosulfonic acid. The resulting compound, which has the formula CHI forms a mono or di salt with organic and inorganic bases.

If two moles of chiorosulfonic acid are used bis-2-alpha-suliatolieptane phosphinic acid is obtained.

Example 3-1 (mixed) aylyl-l-sulfatohearadecz l- I-phosphinic acid sodium salt One mole of (mixed) l-xylyl-l-hydroxypentadecyl-l-phosphinic acid is treated as in Example 1 with one mole of sulfuryl chloride. When no more acid chloride is evolved aqueous sodium carbonate is added in suflicient quantity to hydrolyze the acid chloride and form the disodium .salt. The product has the formula OSOsNa on 0N8 If in place of the above acid chloride phosphorous trichloride or phosphorous oxychloride is used the corresponding phosphate are obtained.

Other compounds of this type which may be prepared by an analogous procedure are the following. The compounds illustrated by these particular formulae are outstanding in their usefulasaa aso ness as surface-active agents in general and for the uses particularly pointed out above.

19 I %o o-s=o l 0H CIBHII (CHI)! osom --- naphthenyl o=r on i Example 4-1-suljatohexadeczrlphosphinic acid-1 One mole of 1hydroxyhexadecylphosphinic acid-1 is treated in dioxane with dioxane-suliur trioxide molecular complex. The reaction is completed by warming and, if desired, a primary, secondary, or tertiary salt is prepared. The product has the formula I OSOsH 1u zi H o= =(OH): Similarly, bis alpha suliato-l-hexadecylphosphinic acid, having the formula OSOaH C1sHa|-C-PCC1aHai is prepared. Example 5-Dinaphthenylsulfatomethane phosphimc acid sodium salt naphthenyl naphthenyl naphthenyl 0 OK naphthenyl Example 6-Diphenylphosphitonaphthenyl methane phosphinic acid One mole of diphenylnaphthenylhydroxymethane phosphinate is treated in pyridine in the cold with one mole of phosphorous trichloride and warmed on the steam bath to complete the reaction. Then 1.5 moles of sodium carbonate in 2,333,930 3 Water are added and the pyridine is removed un- (8) Bis 1 alpha sidfatododecyinaphthaiene -der reduced pressure. The reaction product has phosphinlc acid the formula: 1 I

o4-on 5 I V O=P 0H v a on -0 v Example 7 H One lz-hydmxy'l-mmxyheptadecane (9) Anthracenylsulfatoheptadecyl methane phosphosphinic acid-12 is reacted, as in Example 1. pmnic acid The product is 12-sulfato-I-carboxyheptadecane v phosphinic acid. If desired the mono, di, and tri 15 080;]! esters of giycerine may be prepared from this .4111! .acid. In place of glycerine any desired carbinol =0 may be used. These esters may be prepared in A the reverse manner, that is, by sulfatlng the esters in place or the free acids. The keto acids (10) Sulfodibenzofurane s uli. a t on aphthenyi needed to prepare the phosphinic acids are pre- 1 methane phosphinic acid pared as described in U. S. Patent 2,178,760. e Using methods described in Examples 1-7, the Z following compounds have been prepared: I Hnaphthenyi 1) 2-sulfatohexane phosphinic' acid-2 osom (11) (C e t y l) Acenaphthenylsuifatocyclohexyb 043w 4 i methane suiflnic acid 3 O=P (OH), CHr-CH: (2) Bis-(2-a1pha-su1fatohexane) phosphinic acid v cetyl- -CH CH:

CH: CH: I CeHr-(J-P- -C4H| W O=P OH GET-CH 0'? OH OH osom 0503K (12) Bis dicarbazyl alpha-suliato-a-hydroxy- (a) Naphthenylbutylsulfatomethane phosphinic tridecylphmphmic acid acid s 0H OSOH 40 -012Ha1 naphthenyP-Cdio N 0: H 0=POH on (4) Naphthenyl 'y ketobutylsuifatomethane phosphinic acid osom e H na hthen id-cnrcnr-ccm (13) l-hydroxy phenyl-bis [2,4 heXadecyLa-suI- o=l -os fate-u suiflnic acid] OH H osoai (5) 2,5-disu1fat0hexane-2,5-diphosphinio acid 1 am 0801K osom t t CHzcH,-cm ?CH| OH 0=P- 0H), O=P(OH)1 H etc.

(6) Z-phdsphito- 5 -sulfatohexane- 2,5 -diphosphinic acid =P-0H or-(onh 0so=H on CH; CHr-CH:-( -CH| Us: or m Comma as Tnxmr: LUBRICANTS O=POH O=P-'(OH): AMI'STATICS 0H Example 8 (7) Tr i 0 PropylbenzoheptadecenylsulffltO The bis-diethylcyclohexylamine salt of 2-su1- methane phosphinic acid fatoheptane-2-phosphinic acid minim-0.11

is applied to a textile material such as silk, wool,

Example 9 90-95 parts butyl naphthenate -5 parts monosodium monoethanolamlne salt of 2 alpha sulfate 2 alpha-hydroxyheptane phosphlnic acid OSOSNE on is applied to textile materials such as silk, wool, cotton, viscose, cellulose acetate, etc., as described in Example 8. If the yarn is intended primarily for knitting, the amount 01' conditioning liquid applied may vary from 2-25% by weight of the yarn and if for weaving, between l5% by weight.

Cellulose acetate filaments treated as described above are quite soft and pliable and give improved results in textile operations such as weaving, knitting, etc., and especially in the preparation of cut staple yarn. Other examples of suitable lubricating mixtures having antistatic properties which are used as illustrated in Examples 8 and 9 follow. 1

Other conditioning liquids particularly useful as an antistatic treatment of cut staple fibers composed of or containing cellulose acetate and other cellulose organic acid esters, and useful for the lubrication, anti-static and other treatment of textile yarns of this type have the composition indicated by the following examples.

Example 10 1-10 parts 0 S O H.triethano1amine ll 3l 0=P0H.triethanolamlne Ha):

(1 (mixed) xylyl-l-sulfatohexadecyl-l-phosphinicfacid'bls-triethanolamine salt) 99-90 parts olive oil Example 11 1-20 parts II O-P-ONa L on I-CnHu .C 0=P OH 0H.ditetrahydroiurturylamlne 1 mixed) 1: l l-lhospbatohexadecyl-l-phosphinlo acid sodium y y d ietrahydroiuriurylamine salt) 99-90 parts olive oil Example 12 1-10 parts 0 S 0 zH-naphthenylamine naphthenyl-C-naphthenyl O= -0H.naphthenylamine (Dinaphtbenylsuliato-metbane bis-naphthenylamlne salt) 99-90 parts mineral oil Example 13 10 parts butyl stearate 89-80 parts mineral oil 1-10 parts H OBO|H.di beta-hydroxyetbylcyclohexylsmine CuHrr-C-P-C-Cuflu H flosldlethylcyclohexylamine (Bis-elplwsuliato-l-hexadecylpbosphlnio acid dietb 1 club lamine-dl-beta-hydroxyethylcyclohexylamlneZ55 an Example 14 1-10 parts OSOiEoIeyIamlne --Ci1Hu 1): O= OH OE (1-tri-isopropylphenyl-l-suiiato-octadecenylphosphinic acid-l-oleylamine salt) 99-90 parts neats foot oil Example 15 99-90 parts blown neats-foot 011 parts Example 16 55 parts sperm oil 5 parts OSOiEcycloheXyIamine OBOiEcycIohexylamine CHP' --CsH|r" -CHI O=POH 0H cyclohexylamine 20 parts butyl naphthenate 5 parts 0 OH OiBr-0 g -Ofldiethylcyclohexylamine 15 parts mineral oil Example 17 68 parts blown sperm oil 2 parts water 20 parts di-beta-methoxyethylsuccinate 10 P rts (BiaZ-sulfamateZ-isopropyl-phosphlnic acid) Example 18 1-10 parts osour.

err-on a o=l o H OILmorpholinc (Naphthylbutylsuliato-metharli ehghggilnicacidpotassium morpho' 1o 99-90 teaseed oil Example 19 140 parts 0 S 0albeta-ethoxy-beta'ethoxyethylamine -cyclohexyl 0H.beta-ethoxy-beta-cthoxyethylamine Phen lcycloh lsulfato-methime hosphinic acid bir y beta-e oxy-beta-ethoxyetgylamine) 30-40 parts blown olive 011 69-50 parts blown neat's toot oil Example 20 (Dinaphthenylsuiiatdmethane phosphinic acid trisodium salt) parts sulionated olive oil Us: or me Comma As DYe-DIsPrRsmo Acm'rs, DYE Assisrmrs AND nu: 1m

Example 22 One pound of 1-methylamino-4-ethylaminoanthraquinone is ground with pound i-phenyl-l-suliatohexadecyl phosphinic acid disodium salt,

OSQsNl and 3 pounds of sugar in a ball mill. The resultin: finely-divided mixture is then added to 100 gallons oi water heated to 60-80 and the resultin: aqueous suspension of blue dye is used to dye about 100 lbs. of cellulose acetate in any desired manner.

Example 23 One pound of p-nitrobenzeneazo ethyl-betahydroxyethyl-aniline is ground in a ball ml with V4 pound of OSOiNa C11Hu 0= P-ONa OH (l-dibutylphenyl-l-suliatooctadecyl phosphinie acid disodium salt) and the finely-divided mixture is added to gallons of water heated to 60-80 and used to dye 100 lbs. of cellulose acetate an orange-red shade.

I Example 24 One pound of NE-om is added to 100 gallons 0! water containing 54.

pound of OBOtNB 'CuHn Then 100 pounds of a woolen fabric is enteredand dyed at 60-90" level deep blue shades, the

' fabric being well wetted out.

In addition to the above-mentioned uses, the,

compounds of our invention are especially efi'ective as detergents for washing textile, china ware, cooking utensils and the like. These compounds may also be employed in place of ordinary soaps for shampooing, shaving and similar applications as well as in tooth paste and other preparations of like character. Their value for these purposes is primarily due to their inertness to hard water and to their chemical stability. Not

only may these materials be employed alone, but

they may also be employed as an adjunct to other detergent and surface-active agents for many industrial and domestic uses.

What we claim is: As new chemical compounds derivatives of phosphonic acid having the structural formula n-o-a' o= -on wherein R and R are substituents selected from the group consisting oi hydrogen, alkyl, aryi,

naphthenyl, and alkaryl.

JOSEPH B. DICKEY. ANTHONY LORIA. 

